CN114804832A - Inorganic nonmetal low-temperature sintered ceramic powder and preparation method thereof - Google Patents
Inorganic nonmetal low-temperature sintered ceramic powder and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of inorganic non-metallic materials, in particular to ceramic powder sintered at low temperature of inorganic non-metal and a preparation method thereof, wherein the raw materials for preparing the ceramic powder comprise, by weight, 35-45 parts of low-melting-point glass powder and 25-35 parts of nucleating agent; the grain size distribution of the ceramic powder is that D50 is 1-3 μm and is in normal distribution. Compared with the prior ceramic sintering process with the temperature of 860-1650 ℃ and the sintering time of 3-16 hours, the low-temperature sintered ceramic powder only needs the low-temperature sintering temperature of 480-780 ℃ and the sintering time of 8-60 minutes; the environment-friendly and energy-saving process for sintering at low temperature for short time can realize firing of ceramic products, is friendly to human body and atmospheric environment, and can save more sintering energy and reduce pollutant emission.
Description
Technical Field
The invention relates to the field of inorganic non-metallic materials, in particular to inorganic non-metallic low-temperature sintered ceramic powder and a preparation method thereof.
Background
Ceramic powder material (ceramic powder for short) is a basic material for manufacturing various ceramics, and is a composite material prepared by mineral separation, grinding, purification, compounding and grading of several large classes of non-metal inorganic mineral substances according to the performance requirements of ceramic materials. The temperature according to the sintering process can be roughly divided into: (1) high-temperature ceramic, wherein the process temperature is 1380-1650 ℃, and the sintering time is 13-16 hours; (2) the medium-temperature ceramic is sintered for 13-16 hours at the process temperature of 1160-1380 ℃; (3) the process temperature of the low-temperature ceramic is 860-1160 ℃, and the sintering time is 3-8 hours. Wherein, the high-temperature ceramic is mainly applied to industrial special ceramics, including electronic components, structural ceramics and the like; medium-temperature ceramics: the method is mainly applied to building and bathroom products; low-temperature ceramics: is mainly applied to daily ceramics, technical ceramics and the like.
The following problems are common in various ceramics at present: (1) the molding process has low yield due to low plasticity; (2) the formula components need higher firing temperature and longer firing time, which brings higher energy cost requirement and lower productivity of a production line; (3) the sintering process at higher temperature and longer time brings high energy consumption and high emission, thereby bringing great pollution and damage to the environment.
Therefore, there is a need to develop an inorganic non-metal low-temperature sintered ceramic powder.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides inorganic nonmetal low-temperature sintered ceramic powder, which comprises the following raw materials, by weight, 35-45 parts of low-melting-point glass powder and 25-35 parts of nucleating agent; the grain size distribution of the ceramic powder is that D50 is 1-3 mu m and the grain size is in normal distribution.
As a preferable technical scheme of the invention, the low-melting-point glass powder comprises 30-45 parts of SiO by weight 2 10-20 parts of Al 2 O 3 20-35 parts of B 2 O 3 5-15 parts of ZnO and 5-9 parts of K 2 O, 3-8 parts of Na 2 O。
In a preferred embodiment of the present invention, the melting start temperature of the low-melting glass frit is 550 ℃.
As a preferable technical scheme of the invention, the linear expansion coefficient of the low-melting-point glass powder is 50 multiplied by 10 measured by a GB/T7320-2018 mandril method -7 -180×10 -7 。
As a preferred embodiment of the present invention, the grain size of the nucleating agent is D50: 1-3 μm.
As a preferred technical solution of the present invention, the nucleating agent is a silicon-containing series nucleating agent.
As a preferable technical scheme of the invention, the nucleating agent is selected from one or more of quartz sand powder, kaolin sand powder and potash feldspar powder sand.
In a preferred embodiment of the present invention, the low melting point glass frit has a particle size distribution such that D50 is 6 to 8 μm and the particle size is normally distributed.
As a preferable technical scheme of the invention, the preparation raw material of the ceramic powder also comprises 20-40 parts by weight of bridging agent.
The second aspect of the present invention provides a method for preparing the inorganic nonmetal low-temperature sintered ceramic powder, comprising: mixing all the preparation raw materials of the ceramic powder, carrying out rod milling and ball milling, then carrying out air cyclone classification, and stirring to obtain the ceramic powder.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, the specific low-melting-point glass powder is adopted, and the particle size distribution of the low-melting-point glass powder is controlled, so that the sintering temperature and the sintering time of the obtained ceramic powder are reduced in the sintering process, and the dimensional stability of the sintered ceramic product is improved;
(2) the nucleating agent with specific particle size and variety is adopted, and is mutually coordinated and promoted with the low-melting-point glass powder, so that the sintering temperature and the sintering time are further reduced, the nucleating agent is particularly used in the fields of small electronic-grade and electric-grade ceramic parts, the sintering temperature is as low as 480 ℃, the sintering time can be as short as 10min, and the mechanical property of the fired ceramic product is excellent;
(3) according to the ceramic powder, a certain bridging agent is added, so that the ceramic firing process and the structural mechanics, dimensional stability and surface flatness of a finished product are improved, and the yield of the product is further improved;
(4) the method adopts the low-melting-point glass powder without heavy metal (lead) and environment-friendly inorganic nonmetal as a carrier, and respectively adopts quartz sand powder, kaolin sand powder, potash-soda feldspar powder sand, zeolite sand powder and wollastonite sand powder which are large in dosage and low in price as nucleating agents and bridging agents to prepare the low-temperature sintered ceramic powder, and compared with the conventional ceramic sintering process with the temperature of 860-doped sand 1650 ℃ and the sintering time of 3-16 hours, the low-temperature sintered ceramic powder only needs the low-temperature sintering temperature of 480-doped sand 780 ℃ and the sintering time of 8-60 minutes; the environment-friendly and energy-saving process for sintering at low temperature for short time can realize firing of ceramic products, is friendly to human bodies and atmospheric environment, and can save more sintering energy and reduce pollutant emission;
(5) the ceramic product fired by the ceramic powder has scientific particle size combination and larger specific surface area, so that higher material plasticity, good manufacturability and good product performance can be obtained, and the ceramic product comprises the following components in percentage by weight:
good plasticity: the ceramic powder sintered at low temperature has the granularity and normal particle size distribution of gold, has good dispersion and smooth forming process and brings higher yield;
lower shrinkage ratio: the ceramic powder sintered at low temperature has enough fineness and the granularity and normal grain size distribution of gold, and the formed product has higher density, reduced shrinkage ratio and better dimensional stability;
good mechanical properties: the fired ceramic product has higher density, good deformation strength, surface hardness, compressive strength, good machining performance and the like;
good color properties: the raw materials of the formula are basically white or white transparent materials, the processing process almost has no secondary pollution, and the obtained ceramic product is a powder product with higher whiteness and is easy to disperse with various toners and to be fired for color development to obtain various color ceramic products required by users;
can be used as a low-temperature sintering carrier of other functional ceramics: because the ceramic product sintered at low temperature is characterized by low-temperature melting, the ceramic product can be used as products such as other functional ceramic carriers, fluxing additives, high-temperature inorganic solvents and the like.
Can be used as a functional filling material of a new ceramic organic composite material: because the ceramic powder product sintered at low temperature is characterized by low-temperature melting, the ceramic powder product can be used as products such as flame-retardant plastics, flame-retardant rubber, fire-resistant organic binders and the like for modification, and the application of the ceramic powder product comprises the following 5 major mechanisms:
(1) reacting with organic free radicals to form incombustible matter;
(2) melting and sealing the mixture into a temperature-resistant layer of a ceramic state/glass state membrane wall structure;
(3) heat absorption and melting into a ceramic state/glass state membrane wall structure oxygen insulation layer;
(4) cooling to form eutectic ceramic state/glass state 'absolute drop crust layer';
(5) the final hard insulating dense (water-tight and gas-tight) ceramic state/glass state stabilizer.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The first aspect of the invention provides inorganic nonmetal low-temperature sintered ceramic powder, which comprises the following raw materials, by weight, 35-45 parts of low-melting-point glass powder and 25-35 parts of a nucleating agent; the grain size distribution of the ceramic powder is that D50 is 1-3 mu m and the grain size is in normal distribution.
D50: the cumulative percent particle size distribution for a sample at 50% corresponds to the particle size. Its physical meaning is that the particle size is greater than 50% of its particles and less than 50% of its particles, D50 also being referred to as the median or median particle size.
In one embodiment, the raw materials for preparing the ceramic powder further comprise 20-40 parts by weight of a bridging agent.
In a preferred embodiment, the raw materials for preparing the inorganic non-metal low-temperature sintered ceramic powder comprise 40 parts by weight of low-melting-point glass powder, 30 parts by weight of nucleating agent and 30 parts by weight of bridging agent.
In one embodiment, the ceramic powder has a particle size distribution such that D50 is 2 μm and the particle size is normally distributed.
Low-melting-point glass powder
Low-melting glass powder: the low-temperature melting glass powder is different from glass powder in production formula raw materials and excellent in functional effect. The low-temperature molten glass powder treated by the silane coupling agent has good compatibility with various resins, good adsorption performance, easy mixing and no agglomeration. The low-melting-point glass powder can obviously improve the performances of yellowing resistance, compression resistance, fracture resistance, permeability resistance, corrosion resistance, impact resistance and wear resistance.
In one embodiment, the low melting point glass frit comprises 30 to 45 parts by weight of SiO 2 10-20 parts of Al 2 O 3 20-35 parts of B 2 O 3 5-15 parts of ZnO and 5-9 parts of K 2 O, 3-8 parts of Na 2 O。
In one embodiment, bismuth oxide, indium oxide and tellurium oxide may be added to the low melting point glass frit in amounts conventionally selected by those skilled in the art as a low temperature fluxing agent.
Preferably, the low-melting glass frit has a melting start temperature of 550 ℃ or lower.
The low-melting-point glass powder can be obtained by 1 or more grades with the initial melting temperature of 330-550 ℃.
Preferably, the linear expansion coefficient of the low-melting-point glass powder is 50 multiplied by 10 measured by a GB/T7320-2018 mandril method -7 -180×10 -7 。
The person skilled in the art can adjust the weight parts of the low-melting glass powder to make the melting start temperature and the linear expansion coefficient of the low-melting glass powder reach the values recorded in the present application.
Coefficient of linear expansion: the physical term, which is sometimes referred to as linear elasticity (linear expansion), indicates the degree of expansion or contraction of a material. The linear expansion coefficient of a certain temperature point and the linear expansion coefficient of a certain temperature interval are divided, and the latter is called an average linear expansion coefficient. The former is the amount of elongation per degree of increase in material per unit length; the average linear expansion coefficient is the average elongation per liter of a material at a temperature interval of one degree higher per unit length.
At present, because the sintering temperature of the ceramic phase is 1400-1900 ℃, in order to reduce the sintering temperature, some glass powders CaO and B with low melting points are added 2 O 3 、SiO 2 、TiO 2 、ZrO 2 、Na 2 O、K 2 O、Li 2 O, etc., however, although the lowest sintering temperature of the ceramic powder obtained at present is at 840-920 ℃ after the low melting point glass powder is added, the sintering time is long, and the addition of the low melting point glass powder in the prior art reduces the forming stability of the product when the ceramic is sintered, the applicant has surprisingly found through a series of experimental designs after research that when the ceramic powder comprises a specific content of SiO 2 、Al 2 O 3 、B 2 O 3 、ZnO、K 2 O、Na 2 O, and controlling the particle size and distribution adjustment of the formula raw materials, for example, the particle size D50 is less than 10 mu m, and the proportion is regulated so that the melting starting temperature of the low-melting-point glass powder is less than or equal to 550 ℃, the lowest melting point can be 330 ℃, and simultaneously the linear expansion coefficient is kept to be 50 x 10 measured by a GB/T7320-2018 push rod method -7 ～180×10 -7 In the interval range, the obtained ceramic powder has a lower sintering temperature lower than 780 ℃, the sintering time is lower than 60min, and the forming stability of the product during sintering is good, the applicant considers that the possible reasons are that the low-melting-point glass powder under the condition has good compatibility with the nucleating agent and the bridging agent in the application and is uniformly dispersed in the sintering process, and in addition, the existence of the low-melting-point glass powder under the condition has uniform crystal form and uniform particle distribution after the ceramic powder is sintered, so that the bulk density of the formula material is large, the thermal conductivity is high, the melting range is short, the density among ceramic molecules is reduced, the shrinkage ratio in the sintering process is reduced, and the forming stability of the ceramic product is easy to control.
In one embodiment, the low melting glass frit is selected from the group consisting of D235, D245, D250, D255 brand low melting glass frits.
In the application, D235, D245, D250 and D255 low-melting-point glass powder is from Anmi micro-nano new material (Guangzhou) Co.
In one embodiment, the low melting point glass frit has a particle size distribution such that D50 is 6 to 8 μm and the particle size is normally distributed.
Those skilled in the art can ball mill the D235, D245, D250 and D255 low-melting-point glass powder to obtain the low-melting-point glass powder with D50 of 6-8 μm and normally distributed particle size.
Preferably, the low melting point glass frit has a particle size distribution such that D50 is 6 μm and the particle size is normally distributed.
Nucleating agent
In one embodiment, the nucleating agent is a silicon-containing series nucleating agent.
Preferably, the nucleating agent is selected from one or more of quartz sand powder, kaolin sand powder and potash-sodalite sand.
Quartz powder: quartz powder (quartz sand) also called silica micropowder is a silicate mineral with hardness, wear resistance and stable chemical properties, and the main mineral component of the silicate mineral is SiO 2 . The quartz sand is milky white or colorless and semitransparent, has the hardness of 7, is crisp and not cleaved, has conchoidal fracture, grease luster and bulk density (20-200 meshes are 1.5), has obvious anisotropy in chemical, thermal and mechanical properties, is insoluble in acid, is slightly soluble in KOH solution and has the melting point of 1650 ℃. After quartz stone extracted from mines is processed, a product with fineness below 120 meshes (smaller than 120 meshes) is generally called quartz sand. The product exceeding 120 meshes is called quartz powder.
Kaolin: kaolin is a non-metallic mineral, a clay and claystone based on clay minerals of the kaolinite group. It is also called dolomitic soil because it is white and fine. The name is obtained from Kaolin village in Jingdezhen of Jiangxi province.
The pure kaolin is in a white, fine and soft soil shape and has good physical and chemical properties such as plasticity, fire resistance and the like. The mineral components of the mineral composition mainly comprise kaolinite, halloysite, hydromica, illite, montmorillonite, quartz, feldspar and other minerals. Kaolin has wide application, is mainly used for paper making, ceramics and refractory materials, is used for coating, rubber filler, enamel glaze and white cement raw materials, and is used for industrial departments such as plastics, paint, pigment, grinding wheels, pencils, daily cosmetics, soap, pesticide, medicine, textile, petroleum, chemical industry, building materials, national defense and the like in a small amount.
The feldspar is alkali metal or alkaline earth such as potassium, sodium, calcium, barium, etcThe crystal structure of the metal aluminosilicate mineral belongs to a framework structure. The main component of the material is SiO 2 、Al 2 O 3 、K 2 O、Na 2 O, CaO, etc.
Potassium feldspar (orthoclase) with molecular formula of K 2 O·Al 2 O 3 ·6SiO 2 。
Albite (canadian) with molecular formula of Na 2 O·Al 2 O 3 ·6SiO 2 。
Preferably, the grain diameter of the nucleating agent is D50 and is 1-3 μm; more preferably, the grain size of the nucleating agent is D50 of 2 μm.
At present, ZrO is mostly used in ceramic powder 2 、TiO 2 As nucleating agents, however ZrO 2 、TiO 2 The applicant has surprisingly found that when the nucleating agent is selected from one or more of quartz sand powder, kaolin sand powder and potash-soda feldspar powder sand, the grain size is controlled to be 800-2500 meshes, and the grain size of the ceramic powder is ground and controlled to be D50 of 1-3 mu m and normally distributed, the sintering temperature can be as low as 480 ℃ and the sintering time can be as short as 10min in the sintering process, so that the ceramic powder has significant advantages compared with the conventional sintering temperature and sintering time, and the applicant considers that the possible reason is the nucleating agent with the specific grain size and the grain size distribution of the ceramic powder, in the sintering process, the ceramic powder particles have certain smooth property, in the low-temperature sintering process, the nucleating agent particles can be attracted and contacted with the low-melting-point glass powder and the bridging agent in time, and the particles are in contact connection through a rolling shaft to play a nucleating function, so that the ceramic powder particles can be refined in the sintering process by the nucleating agent, crystallization is accelerated, and the forming time is short and stable at a lower sintering temperature. .
Applicants have unexpectedly found that when the low melting point glass frits of the present application have an onset melting temperature of less than or equal toAt 550 ℃, and the linear expansion coefficient is 50 multiplied by 10 measured by a GB/T7320-2018 mandril method -7 -180×10 -7 And meanwhile, when the nucleating agent is one or more of quartz sand powder, kaolin sand powder and potash-soda feldspar powder sand with the particle size of D50 of 1-3 mu m, and the low-melting-point glass powder is continuously ball-milled into low-melting-point glass powder particles with the particle size distribution of D50 of 6-8 mu m and normal distribution in the preparation process of the ceramic powder, the mechanical strength of the obtained ceramic product is greatly increased.
Bridging agent
In one embodiment, the bridging agent is selected from one or more of zeolite sand powder, wollastonite sand powder, glass powder and glass fiber powder.
Preferably, the particle size of the bridging agent is D50 and is 3-5 μm; more preferably, the particle size of the bridging agent is D50 and is 4-5 μm.
In order to improve the flatness of the surface of the sintered ceramic, the particle size D50 of the ceramic powder is reduced to about 2 μm, the fineness of the molecules is reduced, and the surface is relatively flat, however, in the present application, the particle size distribution of the ceramic powder is D50 to 1-3 μm, the particle size is normally distributed, the particle size distribution is large, and the particle size distribution is uneven compared with the prior art, and the flatness of the surface of the ceramic is affected after sintering, the applicant combines the beauty and the practical value of the ceramic, and unexpectedly finds that when some bridging agent with the particle size of D50 to 3-5 μm is added, and the bridging agent is zeolite sand powder and/or wollastonite sand powder, the flatness of the surface of the sintered ceramic is greatly improved, and the applicant thinks that the bridging agent with the specific particle size in the present application is easy to connect in the concave position of the ceramic molecule, and the particle size is just filled with the concave height, meanwhile, the material cannot be stacked at the protruding height, so that the flatness is improved.
The second aspect of the present invention provides a method for preparing an inorganic non-metal low-temperature sintered ceramic powder, comprising: mixing all the preparation raw materials of the ceramic powder, carrying out rod milling and ball milling, then carrying out air cyclone classification, and stirring to obtain the ceramic powder.
In one embodiment, the method for preparing the inorganic non-metallic low-temperature sintered ceramic powder comprises the following steps:
(1) adding low-melting-point glass powder into a horizontal spiral ribbon mixer with balanced specific gravity, and carrying out homogeneous mixing to obtain a semi-finished product A; conveying the semi-finished product A to a ball mill by a screw rod for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 6-8 mu m after air cyclone classification; stirring the semi-finished product B by a horizontal type ribbon mixer with balanced specific gravity for 10min to obtain a low-melting-point glass powder carrier;
(2) putting the low-melting-point glass powder carrier into a horizontal ribbon mixer with balanced specific gravity (wherein, the nucleating agent and the bridging agent are sequentially added, and stirring uniformly to obtain a semi-product C;
(3) conveying the semi-product C to a ball mill by a screw for ball milling and powdering, and obtaining a normally distributed semi-product D with the granularity D50 of 1-3 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal type ribbon mixer with balanced specific gravity to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
The ball mill in the application is a TCIQM horizontal ball mill of the great industry machinery company, and the horizontal spiral ribbon balanced specific gravity mixer is a Xin mechanical WL-1000.
In a preferred embodiment, the method for preparing the inorganic non-metallic low-temperature sintered ceramic powder comprises the following steps:
(1) adding low-melting-point glass powder into a horizontal spiral ribbon mixer with balanced specific gravity, and carrying out homogeneous mixing to obtain a semi-finished product A; conveying the semi-finished product A to a ball mill by a screw for continuous ball milling, and obtaining a normally distributed semi-finished product B with the granularity D50 of 7 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer to obtain a low-melting-point glass powder carrier;
(2) putting the low-melting-point glass powder carrier into a horizontal ribbon mixer with balanced specific gravity, sequentially adding a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a ball mill by a screw for continuous rod milling and ball milling, and obtaining a normally distributed semi-product D with the granularity D50 of 5 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Example 1
The embodiment 1 of the invention provides an inorganic nonmetal low-temperature sintered ceramic powder, which comprises the following raw materials in parts by weight: 35 parts of low-melting-point glass powder, 25 parts of nucleating agent and 20 parts of bridging agent.
The low-melting-point glass powder is a D235 product with the melting temperature of 350 ℃ from Anmi micro-nano new material (Guangzhou) Limited company; the nucleating agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 2.14 μm nucleating agent powder, product No. GT 18; the bridging agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 4.76 μm of glass powder with the mark of T803.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding low-melting-point glass powder into a horizontal spiral ribbon mixer with balanced specific gravity, and carrying out homogeneous mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the particle size D50 of 6 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting a low-melting-point glass powder carrier into a horizontal ribbon mixer (Xin machine WL-1000), sequentially putting a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-product D with the granularity D50 of 1 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Example 2
The embodiment 2 of the invention provides inorganic nonmetal low-temperature sintered ceramic powder, which comprises the following raw materials in parts by weight: 45 parts of low-melting-point glass powder, 35 parts of nucleating agent and 40 parts of bridging agent.
The low-melting-point glass powder is a D245 brand product with the melting temperature of 450 ℃ from Anmi micro-nano new material (Guangzhou) company Limited; the nucleating agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 2.14 μm nucleating agent powder, product No. GT 18; the bridging agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 4.76 μm of glass powder with the mark of T803.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding low-melting-point glass powder into a horizontal spiral ribbon mixer with balanced specific gravity, and carrying out homogeneous mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of a Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 8 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting a low-melting-point glass powder carrier into a horizontal ribbon mixer (Xin machine WL-1000), sequentially putting a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-product D with the granularity D50 of 3 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Example 3
The embodiment 3 of the invention provides inorganic nonmetal low-temperature sintered ceramic powder, which comprises the following raw materials in parts by weight: 40 parts of low-melting-point glass powder, 30 parts of nucleating agent and 30 parts of bridging agent.
The low-melting-point glass powder is a D250 product with the melting temperature of 500 ℃ from Anmi micro-nano new material (Guangzhou) company Limited; the nucleating agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 2.14 μm nucleating agent powder, product No. GT 18; the bridging agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 4.76 μm of glass powder with the mark of T803.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding the low-melting-point glass powder into a horizontal spiral ribbon balanced specific gravity mixer (Xin machine WL-1000), and uniformly mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 7 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting the low-melting-point glass powder carrier into a horizontal ribbon mixer with balanced specific gravity, sequentially adding a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-product D with the particle size D50 of 2 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Example 4
Embodiment 4 of the present application provides an inorganic non-metal low-temperature sintered ceramic powder, which is prepared from the following raw materials in parts by weight: 40 parts of low-melting-point glass powder, 30 parts of nucleating agent and 30 parts of bridging agent.
The low-melting-point glass powder is a D70 product with the melting temperature of 700 ℃ from Innovative Material Co., Ltd, in Foshan city; the nucleating agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 2.14 μm nucleating agent powder, product No. GT 18; the bridging agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 4.76 μm of glass powder with the mark of T803.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding low-melting-point glass powder into a horizontal type spiral ribbon mixer with balanced specific gravity, and uniformly mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 7 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting a low-melting-point glass powder carrier into a horizontal ribbon mixer (Xin machine WL-1000), sequentially putting a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of a Daiko mechanical company by a screw rod for ball milling and powder making, and obtaining a normally distributed semi-product D with the particle size of D50 being 2 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Example 5
Embodiment 5 of the present application provides an inorganic non-metal low-temperature sintered ceramic powder, which is prepared from the following raw materials in parts by weight: 40 parts of low-melting-point glass powder, 30 parts of nucleating agent and 30 parts of bridging agent.
The low-melting-point glass powder is a D250 product with the melting temperature of 500 ℃ from Anmi micro-nano new material (Guangzhou) company Limited; the nucleating agent is from New Dongcuan New materials Co, Ltd, and has the particle size of D50: 17 μm silica micropowder product; the bridging agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 4.76 μm of glass powder with the mark of T803.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding the low-melting-point glass powder into a horizontal spiral ribbon balanced specific gravity mixer (Xin machine WL-1000), and uniformly mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 7 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting the low-melting-point glass powder carrier into a horizontal ribbon mixer with balanced specific gravity, sequentially adding a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-product D with the particle size D50 of 2 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Example 6
Embodiment 6 of the present application provides an inorganic non-metal low-temperature sintered ceramic powder, which is prepared from the following raw materials in parts by weight: 40 parts of low-melting-point glass powder, 30 parts of nucleating agent and 30 parts of bridging agent.
The low-melting-point glass powder is a D250 product with the melting temperature of 500 ℃ from Anmi micro-nano new material (Guangzhou) company Limited; the nucleating agent is derived from a particle size D50 of an Ammi micro-nano new material (Guangzhou) Co Ltd: 2.14 μm nucleating agent powder, product No. GT 18; the bridging agent is derived from Innovative materials, Inc. of Foshan city, and has a particle size of D50: 5 μm R-30 product.
The preparation method of the inorganic nonmetal low-temperature sintered ceramic powder comprises the following steps:
(1) adding the low-melting-point glass powder into a horizontal spiral ribbon balanced specific gravity mixer (Xin machine WL-1000), and uniformly mixing to obtain a semi-finished product A; conveying the semi-finished product A to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-finished product B with the granularity D50 of 7 mu m after air cyclone classification; stirring the semi-finished product B for 10min by a horizontal ribbon balanced specific gravity mixer (Huanxin machine WL-1000) to obtain a low-melting-point glass powder carrier;
(2) putting the low-melting-point glass powder carrier into a horizontal ribbon mixer with balanced specific gravity, sequentially adding a nucleating agent and a bridging agent, and uniformly stirring to obtain a semi-product C;
(3) conveying the semi-product C to a TCIQM horizontal ball mill of Dai mechanical company by a screw for ball milling and powder making, and obtaining a normally distributed semi-product D with the particle size D50 of 2 mu m after air cyclone classification;
(4) and (3) uniformly mixing the semi-product D by a horizontal ribbon balanced specific gravity mixer (Xin mechanical WL-1000) to obtain the inorganic nonmetal low-temperature sintered ceramic powder.
Performance evaluation
1. Firing appearance: the inorganic non-metal low-temperature sintered ceramic powders obtained in examples 1 to 6 were used to fire ceramic products, respectively, wherein the firing process was as follows:
(1) weighing 100 g of materials according to the experimental formula, adding the materials into a beaker, and stirring the materials by using a glass cup until a homogeneous sample 1 is obtained;
(2) injecting 12.5 g of the stirred homogeneous sample into a 10mm wafer printing mold, and filling and compacting for 3 times to obtain a sample 2;
(3) placing the sample 2 on a high-temperature ceramic slide for a test, and drying the sample in a constant-temperature drying furnace at 160 ℃ for 10min to obtain a sample 3;
(4) putting the sample 3 into a muffle furnace which is heated to 650 ℃ and sintering for 30min, and taking out to obtain a sample 4;
(5) repeatedly baking for 15 times to obtain the final product. The fired appearance quality was recorded separately.
2. Shrinkage ratio: the inorganic nonmetallic low-temperature-sintered ceramic powders obtained in examples 1 to 6 were used to fire ceramic products in the same manner as in example 4.1, and the shrinkage ratio was recorded (R) (%) Before firing -R After firing )/R Before firing X 100% and R is the radius.
3. Mechanical properties: the ceramic products were fired using the inorganic non-metallic low-temperature sintered ceramic powders obtained in examples 1 to 6, respectively, wherein the firing process was the same as that of 4.1, and the fired ceramic products were tested for flexural strength by a three-point bending method using a SANS Universal testing machine, with a target value of > 195 MPa.
4. Density: the fired ceramic products obtained in examples 1-6 were tested by a ceramic densitometer model XFMMD-3205A.
TABLE 1
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The inorganic non-metal low-temperature sintered ceramic powder is characterized in that the preparation raw materials comprise, by weight, 35-45 parts of low-melting-point glass powder and 25-35 parts of nucleating agent; the grain size distribution of the ceramic powder is that D50 is 1-3 mu m and the grain size is in normal distribution.
2. The inorganic non-metallic low-temperature sintered ceramic powder according to claim 1, wherein the low-melting glass powder comprises 30 to 45 parts by weight of SiO 2 10-20 parts of Al 2 O 3 20-35 parts of B 2 O 3 5-15 parts of ZnO and 5-9 parts of K 2 O, 3-8 parts of Na 2 O。
3. The inorganic non-metallic low-temperature sintered ceramic powder according to claim 2, wherein the low-melting glass powder has an initial melting temperature of 550 ℃ or less.
4. The inorganic non-metal low-temperature sintered ceramic powder according to claim 3, wherein the linear expansion coefficient of the low-melting-point glass powder is 50 x 10 measured by GB/T7320-2018 push rod method -7 -180×10 -7 。
5. The inorganic non-metallic low-temperature sintered ceramic powder according to any one of claims 1 to 4, wherein the grain size of the nucleating agent is D50: 1-3 μm.
6. The inorganic non-metallic low-temperature sintered ceramic powder of claim 5, wherein the nucleating agent is a silicon-containing series nucleating agent.
7. The inorganic non-metallic low-temperature sintered ceramic powder of claim 6, wherein the nucleating agent is selected from one or more of quartz sand powder, kaolin sand powder and potash-soda feldspar powder sand.
8. The inorganic non-metallic low-temperature sintered ceramic powder according to claim 6 or 7, wherein the low-melting glass powder has a particle size distribution such that D50 is 6 to 8 μm and the particle size is normally distributed.
9. The inorganic non-metallic low-temperature sintered ceramic powder of claim 8, wherein the raw materials for preparing the ceramic powder further comprise 20 to 40 parts by weight of a bridging agent.
10. A method for preparing the inorganic non-metallic low-temperature sintered ceramic powder according to any one of claims 1 to 9, comprising: mixing all the preparation raw materials of the ceramic powder, classifying by air cyclone after rod milling and ball milling, and stirring to obtain the ceramic powder.
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